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Synlett 2020; 31(16): 1613-1618
DOI: 10.1055/s-0040-1707196
DOI: 10.1055/s-0040-1707196
letter
Room-Temperature Palladium(II)-Catalyzed Direct 2-Arylation of Indoles with Tetraarylstannanes
Authors
We are grateful for the financial support of the National Natural Science Foundation of China (21902126), China Postdoctoral Science Foundation (2019M663947XB), and the 111 Project (B14041).
Further Information
Publication History
Received: 04 May 2020
Accepted after revision: 14 June 2020
Publication Date:
05 August 2020 (online)
Abstract
A palladium(II)-catalyzed direct 2-arylation of indoles by tetraarylstannanes with oxygen (balloon) as the oxidant at room temperature has been developed. Various tetraarylstannanes can be employed as aryl sources for 2-arylation of indoles in up to 89% yield, providing a practical and efficient catalytic protocol for accessing 2-arylindoles.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707196.
- Supporting Information (PDF)
-
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1-Methyl-2-Phenyl-1H-indole (3a); Typical Procedure
A Schlenk tube equipped with a magnetic stirrer bar was charged with N-methylindole (1a; 0.5 mmol, 1.0 equiv), Ph4Sn (2a; 0.19 mmol), and (MeCN)2Pd(OTs)2 (10 mol%, 0.05 mmol). HOAc (5 mL) was then introduced by using a syringe. The tube
was degassed (×3) then charged with O2, and the O2 atmosphere was maintained by using a balloon. The mixture was then stirred at 25 °C
for 12 h. The HOAc was removed by rotary evaporation, and the residue was dissolved
in CH2Cl2 (50 mL) and the solution was washed with aq NaHCO3 (2 × 30 mL). The organic layers were combined, washed with brine, and dried (Na2SO4). The solvent was removed by rotary evaporation, and the crude product was purified
by column chromatography (silica gel, PE–CH2Cl2) to give a white solid; yield: 89 mg (86%); mp 67.5–69.5 °C; Rf
= 0.2 (PE–CH2Cl2, 10:1).
1H NMR (300 MHz, acetone-d
6): δ = 7.59–7.57 (m, 3 H), 7.50–7.48 (m, 2 H), 7.43 (d, J = 7.8 Hz, 2 H), 7.20 (t, J = 7.2 Hz, 1 H), 7.18 (t, J = 7.2 Hz, 1 H), 6.55 (s, 1 H), 3.75 (s, 3 H).13C NMR (75 MHz, acetone-d
6): δ = 141.9, 139.2, 133.4, 129.7, 129.1, 128.7, 128.4, 122.0, 120.8, 120.1, 110.3,
101.9, 31.1. HRMS (ESI); m/z [M + Na]+ calculated for C15H13NNa: 230.0946; found: 230.0948.
1-Methyl-2-(4-tolyl)-1H-indole (3b)
White solid; yield: 88 mg (80%); mp 97.5–100.5 ℃; Rf
= 0.2 (PE–CH2Cl2, 10:1). 1H NMR (300 MHz, acetone-d
6): δ = (m, 1 H), 7.48–7.40 (m, 3 H), 7.33–7.31 (m, 2 H), 7.18 (t, J = 7.2 Hz, 1 H), 7.07 (t, J = 7.2 Hz, 1 H), 6.50 (s, 1 H), 3.75 (s, 3 H), 2.40 (s, 3 H). 13C NMR (75 MHz, acetone-d
6): δ = 142.0, 139.1, 138.2, 130.5, 129.7, 129.3, 128.8, 120.6, 120.4, 120.1, 110.3,
101.5, 31.1, 20.9. HRMS (ESI); m/z [M + Na]+ calculated for C16H15NNa: 244.1102; found: 244.1104.
Characterization data for other products are reported in the SI.
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For examples of transition-metal-catalyzed C–H functionalizations, see: